The flotation of wolframite using sodium hydroxamate as collector was investigated. The collector-mineral interactions were studied by determining collector adsorption, measuring zeta potentials, acquiring infrared spectra and conducting solution chemistry calculations. A multilayer collector adsorption was determined to be necessary for effective flotation and the metal hydroxamate was identified as the major adsorbed species on wolframite. The optimal flotation condition (pH and collector concentrations) observed experimentally agreed well with that predicted from solution chemistry calculations. The calculation also predicted a wider pH range of effective flotation with increasing collector concentrations.